CN102399515B - Curing agent for protein adhesive, and preparation method and application of curing agent - Google Patents
Curing agent for protein adhesive, and preparation method and application of curing agent Download PDFInfo
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- CN102399515B CN102399515B CN 201110401679 CN201110401679A CN102399515B CN 102399515 B CN102399515 B CN 102399515B CN 201110401679 CN201110401679 CN 201110401679 CN 201110401679 A CN201110401679 A CN 201110401679A CN 102399515 B CN102399515 B CN 102399515B
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Abstract
The invention discloses a preparation method for a curing agent for a protein adhesive. The preparation method comprises the following steps of: mixing acid and amine in water; performing first reaction to obtain a water-soluble high molecular solution; and performing second reaction on the water-soluble high molecular solution and anhydride to obtain the curing agent for the protein adhesive. The curing agent for the protein adhesive, which is prepared by the method, is a water-soluble system, is environment-friendly, has high compatibility with the protein adhesive and can achieve the ideal curing effect with small using amount, and the solid content of the curing agent can be regulated according to the requirement. The curing agent for the protein adhesive can be applied to the preparation of a soybean protein adhesive. The prepared soybean protein adhesive is convenient to use and has high bonding strength and water tolerance. In the prepared wood gluing product, formaldehyde release is avoided, and the type II wet strength is more than 0.7 MPa; the wood gluing product has potential of replacing urea-formaldehyde glue; and further popularization and utilization are facilitated.
Description
Technical field
The present invention relates to the solidifying agent field, be specifically related to solidifying agent of a kind of protein gluing agent and its preparation method and application.
Background technology
China is wood-processing industry to the industry of sizing agent demand maximum, the sizing agent of the annual consumption of wood-processing industry accounts for about 60% of total gluing dosage, and the adhesive for wood on the market mainly is " three-aldehyde glue " (urea-formaldehyde glue, phenolic glue, carbamide glue).The raw material of " three-aldehyde glue " all comes from the Chemicals such as oil, and resource-constrained is non-renewable; In addition, " three-aldehyde glue " goods can discharge the free aldehyde of the 1st class carcinogenic substance in production and use procedure, easily cause people's breathing discomfort and the pain of eyes and throat, and serious harm industrial worker and human consumer's is healthy.(Formaldehyde Standards for Composite Wood Act) is formally effective on January 3rd, 2011 for " the Wood composite products formaldehyde standard bill " of the U.S., and the formaldehyde content in the Wood composite products is strict with.The enforcement of this bill will impact the wood gluing goods export enterprise of China, and therefore the formaldehyde in the wood gluing goods, utilize the non-petroleum base renewable resources to prepare environmentally friendly nontoxic sizing agent and be significant mainly from sizing agent.
In natural reproducible resource, protein, starch, lignin etc. can be used for preparing sizing agent.Wherein, the agent of protein gluing is easy to modify and processes, thereby has caused investigator's broad interest.
In recent years, the investigator utilizes by various means, has effectively improved bonding strength and the water tolerance of protein gluing agent.Take whey-protein as example, the people such as Gao are by adding poly-methane diphenyl vulcabond (p-MDI), polyvinyl alcohol (PVA), polyvinyl acetate (PVA) (PVAc), nano-calcium carbonate, prepare aqueous macromolecule-isocyanate (API) sizing agent of whey-protein base, its dry strength and wet tenacity reach respectively 13.38MPa and 6.81MPa, suitable with commercially available API sizing agent, satisfy in the Japanese JIS K6804-2003 standard requirement of strength (the Zhenhua Gao about structure glue, et al.J.Appl.Polym.Sci.2011,120:220-225).But the aqueous macromolecule-isocyanate of this whey-protein base (API) sizing agent exists the technical problem of shelf lives too short (less than 3 hours).
Take vegetable-protein as example, the people such as Hettiarachchy have improved bonding strength and the water tolerance (Hettiarachchy, N.S.et al.J.Am.Oil.Chem.Soc.1995,72,1461) of soy-protein sizing agent with the alkali modification method; Sun and Bian find than alkali modification better effect (Sun, S.X.and Bian, K.et al.J.Am.Oil.Chem.Soc.1999,76,977) is arranged with urea-modified soy protein adhesives; In other prior aries, also have other properties-correcting agent that soybean adhesive, its is carried out modification, if any trypsinase, Guanidinium hydrochloride, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate etc.Utilize alkali extensin matter to divide period of the day from 11 p.m. to 1 a.m protein often can be hydrolyzed; thereby protein molecule is caused certain destruction; bonding strength and water tolerance to the soy-protein sizing agent improve poor effect; other properties-correcting agent is to utilize these small molecules properties-correcting agent that the soy-protein molecular stretching is unlikely to destroy protein molecule; but it is still limited to improve effect, does not reach the requirement of industrialization.
In addition, utilize the soy-protein sizing agent of small molecules reagent modification to have the problem that solid content is low, water tolerance is not good, solid content is low must to cause wood-based plate to produce more energy consumption for dry moisture in making processes, and bonding strength and water tolerance are not good.For example, the patent No. be ZL200710072642.2, the name be called in the patent of invention of " tannic acid modified bean powder adhesion agent and preparation method thereof ", disclose a kind of tannic acid modified bean powder sizing agent that obtains that utilizes, made by the bean powder of 100 weight parts, the water of 600 weight parts and the Weibull of 2～14 weight parts; The patent No. is that ZL 200710072643.7, name are called in the patent of invention of " boric acid modified bean powder adhesive and preparation method thereof ", disclose a kind of boric acid modified bean powder sizing agent that obtains that utilizes, made by the bean powder of 100 weight parts, the water of 600 weight parts and the boric acid of 2～14 weight parts; In above-mentioned two China's patent, its bean powder only accounts for 14.0%～14.2% of bean powder sizing agent weight, and the bean powder sizing agent all is being no more than 0.66MPa at the glued board sample through 30 ℃ of water soaking 2h, the shearing resistance of 63 ℃ of oven dry behind the 1h.
Although blend can improve the water tolerance of soy-protein sizing agent, can not break away from using and discharging of formaldehyde with " three-aldehyde glue ".For example, the method of Wescott and Frihart employing and phenol and aldehyde copolymerization has prepared the sizing agent dispersion system of soybean protein, wherein, the consumption of bean powder can account for 70% of system solid content, can make the cost 20%～40% of general phenolic glue, the sizing agent dispersion of this acidity not only presents good water tolerance, and reach more than 20 days working life, can be used for bonding outdoor use sheet material or preparation composite wood (Wescott J., Frihart C.US patent, US 7345136).
(Li, K.et al.J.Am.Oil.Chem.Soc.2004,8,487 such as Li; The US patent application, US2006/0156954A 1) with cation superpolymer-Polyamide Polyamine Epichlorohydrin Resin (PAE), with the soy-protein effect, also improved to a great extent bonding strength and water tolerance.PAE is wet strengthening resin, is widely used in Pulp industry, and PAE is the cation superpolymer that water-soluble polymeric amide polyamine and epichlorohydrin reaction form, contain active heterocyclic butyl functional group, this functional group can react with the functional group that contains reactive hydrogen, for example ,-COOH ,-OH ,-NH
2Deng, reaction produces preferably cross-linked network structure of water tolerance, and the adding of PAE has improved the water tolerance of soy-protein sizing agent greatly.Li is improved on the basis of above patent has again obtained Canadian Patent CA2458159, this patent with bean powder and PAE as starting material, under alkaline hydrated oxide or borate effect to reach the requirement of water tolerance.More than used PAE solid content lower, large usage quantity causes the soy-protein sizing agent cost that makes higher.(the International Journal ofAdhesion﹠amp such as Liu and Huang; Adhesives.2007,27,59-67; J.Am.Oil.Chem.Soc.2008,85:63-70) utilize the compound linking agent as the soy-protein sizing agent of maleic anhydride and polymine (PEI), action effect can compare favourably with PAE, but PEI is expensive, is unfavorable for the industrialization of soy-protein sizing agent.
Summary of the invention
To have protein gluing agent poor water resistance now and can not thoroughly break away from the problem that formaldehyde discharges in order to solve, thereby the solidifying agent of a kind of protein gluing agent is provided.
The invention provides the preparation method of the solidifying agent of a kind of protein gluing agent, its preparation process is simple and easy to control, and product is stable.
The preparation method of the solidifying agent of a kind of protein gluing agent may further comprise the steps:
1) after being mixed, acid and amine obtains water-soluble polymer solution through the first reaction in water;
Described acid is Pidolidone, L-TARTARIC ACID, FUMARIC ACID TECH GRADE, L-Aspartic acid, maleic acid, 2-oxoglutaric acid, L-hydroxysuccinic acid, methylene-succinic acid, D-2-aminoadipic acid, L-2-aminoadipic acid, 2, the compound of 2-dimethylated pentanedioic acid, Methylpropanedioic acid or formula I structure;
Wherein, the m among the formula I is 0～9 integer;
Described amine is the compound of formula II structure or formula III structure;
Formula II; Formula III;
Wherein, the n among the formula II is 1～700 integer; X is 1～10 integer in the formula III, and y is 1～10 integer;
2) with step 1) water-soluble polymer solution that obtains and acid anhydrides obtain the solidifying agent of protein gluing agent through the second reaction.
In order to obtain better invention effect, below as of the present invention preferred:
Step 1) in, (amino (NH COOH) and in the amine of carboxyl in the described acid
2) mol ratio be 0.5～1: 1, the first reaction conditions: at 120 ℃～190 ℃ lower reaction 1h～3h.During by the first reaction polycondensation synthetic macromolecule resin, the mol ratio that must accurately control reactive group in the raw material is 1: 1, the water-soluble polymer that synthesizes among the present invention, and without the need for high molecular weight, but it is amino that synthetic macromolecule resin need to remain with abundant end, so that the protein gluing agent that adds solidifying agent of the present invention when hot-press solidifying with acid anhydrides formation crosslinking structure, thereby the time-NH that feeds intake
2Excessive; But, if in the amine-NH
2Excessive too many, product can only form low-molecular-weight performed polymer, and this performed polymer can not form enough strong cross-linked structure when protein gluing agent hot-press solidifying, be unfavorable for improving bonding strength and the water tolerance of protein gluing agent.Thereby, (amino (NH COOH) and in the amine of carboxyl in the acid when feeding intake
2) mol ratio be 0.5～1: 1, so not only guaranteed sufficiently high molecular weight but also kept abundant end amino.In addition, the first reaction of the present invention is the reaction of synthetic macromolecule resin, is dehydration reaction, and reaction system need in time dewater, in order to improve molecular weight.Thereby the temperature of reaction of selection must be conducive to that evaporation of water removes in the system, the reaction times that when the temperature of selecting is on the low side, need to grow, during temperature drift power consumption too large, consider, the selective reaction condition is 120 ℃～190 ℃ lower reaction 1h～3h.
Described acid be preferably hexanodioic acid (compound of structure, m=4).Select m＜4 o'clock, during the compou nd synthesis water-soluble polymer of formula I structure, on the high polymer main chain-CH
2-few, so that the hydrophobicity of solidifying agent is relatively poor, thereby limited to the reinforced effects of the water tolerance of protein gluing agent; Select m＞4 o'clock, the compound of formula I structure, price comparison is expensive.Triethylene tetramine (compound of formula II structure, n=2), tetraethylene pentamine (compound of formula II structure, n=3), five ethene hexamines (compound of formula II structure, n=4) etc. amine substance has clear and definite molecular structure, price is more expensive.The compound of formula III structure is polyethylene polyamine, is the co-product of quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines and rare seven amine of six second.The structure of polyethylene polyamine is uncertain, and x and y are uncertain in the formula III, is generally 1～10 integer.Polyethylene polyamine low price and abundant side-NH is arranged
2, form cross-linked network structure when this is conducive to protein gluing agent hot-press solidifying.Described amine is preferably polyethylene polyamine (compound of formula III structure).
The first reaction finishes rear or/and add water in the second reaction.After the first reaction finishes, in order to process the first reaction product and according to the needs of solid content, to add a certain amount of water.In the second reaction, the viscosity of the proportioning of the solid content of solidifying agent and protein-based thing and the agent of protein gluing is added a certain amount of water according to the present invention.
Step 2) in, described acid anhydrides is MALEIC ANHYDRIDE, Succinic anhydried, trimellitic acid 1,2-anhydride, norbornene dicarboxylic anhydride, the naphthalene acid anhydride, dimethyl maleic anhydride, Pyroglutaric acid, the diethylene triamine pentacetic acid (DTPA) dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, methylene radical tetrahydrophthalic anhydride in the methyl, tetrahydrophthalic anhydride, the tetrachloro-phthalic acid acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid anhydride, the 2-methyl maleic anhydride, HHPA, the chlorination trimellitic acid 1,2-anhydride, the phenylsuccinic acid acid anhydride, diacetyl oxide, in the Tetra hydro Phthalic anhydride one or more.Step 1) water-soluble polymer that obtains in can not be separately uses as the solidifying agent of protein gluing agent, need to the material acting in conjunction with binary and the above functional group of binary, form crosslinking structure, bonding strength and the water tolerance of ability Enhancin matter sizing agent; Consider various polyfunctional group materials and-NH
2Reactive behavior, the present invention selects the anhydrides material.Further preferred, described acid anhydrides is MALEIC ANHYDRIDE.Compare with other acid anhydrides, the stability to hydrolysis of MALEIC ANHYDRIDE is better and price is lower.
Amino (NH in described acid anhydrides and the amine
2) mol ratio be 0.2～10: 1, the second reaction conditions: at 20 ℃～70 ℃ lower reaction 1min～30min.The consumption of acid anhydrides is very little the time, and the protein gluing agent that adds solidifying agent of the present invention can not form enough strong cross-linked network structure when hot-press solidifying, thereby reinforced effects is limited; When the consumption of acid anhydrides was too many, unnecessary acid anhydrides did not participate in the formation of crosslinking structure, will be free in the glue-line, and glued board is when poach, and this part free acid anhydrides can enter in the water, thereby effective adhesive substance of glue-line is tailed off, and water tolerance is had disadvantageous effect.20 ℃～70 ℃ lower reaction 1min～30min be for guarantee that acid anhydrides fully dissolves and with step 1) in synthetic water-soluble polymer fully mix.
Step 2) in, adds the aqueous sodium hydroxide solution of 0.5mol/L～1.5mol/L.Alkaline environment is conducive to improve the amine substance reactive behavior, also is conducive to the expansion of protein.
The solidifying agent of the protein gluing agent of described preparation method's preparation, prepared Novel curing agent low-cost, high solids content, use the protein gluing agent after this solidifying agent strengthens, not only do not have formaldehyde release, bonding strength and water tolerance greatly to improve, and be easy to preparation, easy to use.
The present invention also provides the application of the solidifying agent of a kind of protein gluing agent, can be used as solidifying agent and uses, and can be applicable to prepare the agent of protein gluing.
The solidifying agent of described protein gluing agent and protein-based thing mix and blend 5min～60min obtain the agent of protein gluing; Described protein-based thing is one or more in vegetable-protein, whey-protein, casein, the haemproteins.
Further preferred, described vegetable-protein is one or more in legume protein, wheat gluten protein, zein, the cassava crude protein; Described legume protein is a kind of in soybean protein isolate, textured soybean protein, low fat bean powder, the defatted soy flour.Further preferred, described legume protein is defatted soy flour.The protein wt percentage composition of defatted soy flour is about 50%, and price is lower, and application foundation is arranged, and is that the optimum feed stock of commercial application protein gluing agent is selected.
The protein gluing agent of preparation can be used as based Wood Adhesives and uses, its using method is as follows: the method for described protein gluing agent by brushing, spraying or roller coating spread upon on the lignocellulosic material of wanting bonding, can obtain wood-base fibre and particle panel material through colding pressing with hot pressing, described wood-base fibre and particle panel material comprises glued board, shaving board, medium density fibre board (MDF), woodwork plate etc., and simultaneously protein gluing agent also can be used for preparing compoiste wood floor.
Employed solidifying agent among the present invention mainly is to utilize the solidifying agent of protein gluing agent to form cross-linked network structure when hot pressing, thereby improves bonding strength and the water tolerance of the agent of protein gluing.
Compared with prior art, the present invention has the following advantages:
The preparation method of the solidifying agent of protein gluing of the present invention agent, its preparation process is simple, mild condition, controllability is good, and easy handling is easy to suitability for industrialized production, and low production cost has preferably economic benefit and wide application prospect.
The solidifying agent of protein gluing of the present invention agent is water-soluble system, environmental friendliness, and its solid content can be regulated and control with the need, and good with protein gluing agent consistency, less usage quantity just can reach desirable solidification effect.
The solidifying agent of protein gluing of the present invention agent can be applicable to prepare the soy-protein sizing agent, the soy-protein sizing agent of preparation is easy to use, and have preferably bonding strength and a water tolerance, the wood gluing goods that make not only do not have formaldehyde to discharge, and II class wet tenacity is greater than 0.7MPa, have the potentiality that replace urea-formaldehyde glue, be conducive to further utilization and extention.
Embodiment
For technical scheme of the present invention is described better, the spy enumerates following examples, it is emphasized that scope of the present invention not only limits in these embodiments, and these embodiment only are used for describing the present invention.
According to standard GB/T/T 17657-1999 regulation, the strength test of three layers of poplar plate is as follows: three layers of poplar plate through gluing, cold pressing and hot pressing and obtaining, wherein, Amount of spread is 400g/m
2(two-sided) colded pressing under 1.2MPa 30 minutes behind the gluing immediately, then hot pressing, and hot pressing condition: temperature is 140 ℃, and pressure is 1MPa, and hot pressing speed is 80 seconds/millimeter; Three layers of poplar plate after the hot pressing were at room temperature displayed 24 hours, then were sawn into A type sample, namely got dry strength in the test of general-purpose drawing machine.Wet tenacity is that A type sample was soaked 3 hours under 63 ℃, then tests acquisition at the general-purpose drawing machine in ten minutes in the room temperature cooling at once.Dry strength in the embodiment of the invention and the Comparative Examples and wet tenacity all are to record under these conditions.
The solid content test condition: get and weigh after the 0.5g sample places 105 ℃ of baking oven 3h, three groups of parallel surveys are averaged, and the solid content in following examples of the present invention all according to said method records.
Embodiment 1
1) in a 500mL there-necked flask, add 100g water and 39.2g tetraethylene pentamine (be the compound of formula II structure, wherein, n=3), add again the 29.2g hexanodioic acid (for formula I structure, wherein, m=4), obtain mixed solution, mixed solution is placed 190 ℃ of oil baths, worn-out mouthful of reaction 90min, stopped reaction, add 100g water, stir discharging, obtain the solution of water-soluble polymer polymeric amide polyamine, solid content is 44.2%;
2) with step 1) solution of the water-soluble polymer polymeric amide polyamine that obtains all adds in the 2000mL there-necked flask, add again 1000g water and 15g MALEIC ANHYDRIDE, behind 20 ℃ of stirring 10min, drip the NaOH aqueous solution of 120mL 1mol/L, 20 ℃ are stirred 5min, obtain the solidifying agent of protein gluing agent, add again 400g defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirs the 10min discharging, obtain the agent of protein gluing.
The protein gluing agent that obtains is used for the bonding of three layers of poplar plate, and carries out the test of dry strength and wet tenacity, recording respectively dry strength is that 1.88MPa and wet tenacity are 0.78MPa.
Embodiment 2
1) in a 500mL there-necked flask, add 100g water and 43.5g polyethylene polyamine (the formula III structure, chemical pure is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, molecular weight is in 232.38 ,-NH
2Functionality is in 2), add again the 22.2g hexanodioic acid (formula I structure, wherein, m=4), obtain mixed solution, mixed solution is placed 180 ℃ of oil baths, worn-out mouthful of reaction 100min, stopped reaction, add 100g water, stir discharging, obtain the solution of water-soluble polymer polymeric amide polyamine, solid content is 42.3%;
2) with step 1) solution of the water-soluble polymer polymeric amide polyamine that obtains all adds in the 2000mL there-necked flask, add again 1000g water and 15g MALEIC ANHYDRIDE, behind 25 ℃ of stirring 10min, drip the NaOH aqueous solution of 120mL 1mol/L, 25 ℃ are stirred 5min, obtain the solidifying agent of protein gluing agent, add again 400g defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirs the 30min discharging, obtain the agent of protein gluing.
The protein gluing agent that obtains is used for the bonding of three layers of poplar plate, and carries out the test of dry strength and wet tenacity, recording respectively dry strength is that 2.55MPa and wet tenacity are 0.92MPa.
Embodiment 3
1) in a 500mL there-necked flask, add 100g water and 43g polyethylene polyamine (the formula III structure, chemical pure is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, molecular weight is in 232.38 ,-NH
2Functionality is in 2), add again the 25g hexanodioic acid (formula I structure, wherein, m=4), obtain mixed solution, mixed solution is placed 170 ℃ of oil baths, worn-out mouthful of reaction 110min, stopped reaction, add 100g water, stir discharging, obtain the solution of water-soluble polymer polymeric amide polyamine, solid content is 44%.
2) with step 1) solution of the polyphosphazene polymer acid amides polyamine that obtains all adds in the 2000mL there-necked flask, add again 1000g water and 20g MALEIC ANHYDRIDE, behind 35 ℃ of stirring 10min, drip the NaOH aqueous solution of 90mL1mol/L, 35 ℃ are stirred 5min, obtain the solidifying agent of protein gluing agent, add again 400g defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirs the 40min discharging, obtain the agent of protein gluing.
The protein gluing agent that obtains is used for the bonding of three layers of poplar plate, and carries out the test of dry strength and wet tenacity, recording respectively dry strength is that 2.46MPa and wet tenacity are 0.80MPa.
Embodiment 4
1) in a 500mL there-necked flask, add 100g water and 43.5g polyethylene polyamine (the formula III structure, chemical pure is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, molecular weight is in 232.38 ,-NH
2Functionality is in 2), add again the 22.2g hexanodioic acid (formula I structure, wherein, m=4), obtain mixed solution, mixed solution is placed 180 ℃ of oil baths, worn-out mouthful of reaction 100min, stopped reaction, add 100g water, stir discharging, obtain the solution of water-soluble polymer polymeric amide polyamine, solid content is 42.3%.
2) with step 1) solution of the water-soluble polymer polymeric amide polyamine that obtains all adds in the 2000mL there-necked flask, add again 1000g water and 30g trimellitic acid 1,2-anhydride, behind 40 ℃ of stirring 30min, drip the NaOH aqueous solution of 150mL 1mol/L, 40 ℃ are stirred 5min, obtain the solidifying agent of protein gluing agent, add again 400g defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirs the 30min discharging, obtain the agent of protein gluing.
The protein gluing agent that obtains is used for the bonding of three layers of poplar plate, and carries out the test of dry strength and wet tenacity, recording respectively dry strength is that 1.78MPa and wet tenacity are 0.72MPa.
Embodiment 5
1) in a 500mL there-necked flask, add 100g water and 43g polyethylene polyamine (the formula III structure, chemical pure is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, molecular weight is in 232.38 ,-NH
2Functionality is in 2), add again the 22g methylene-succinic acid, obtain mixed solution, mixed solution is placed 190 ℃ of oil baths, worn-out mouthful of reaction 90min, stopped reaction adds 100g water, stirs, discharging obtains the solution of water-soluble polymer polymeric amide polyamine, and solid content is 42.7%.
2) with step 1) solution of the water-soluble polymer polymeric amide polyamine that obtains all adds in the 2000mL there-necked flask, add again 1000g water and 17g pyromellitic acid anhydride, behind 30 ℃ of stirring 30min, drip the NaOH aqueous solution of 150mL 1mol/L, 30 ℃ are stirred 10min, obtain the solidifying agent of protein gluing agent, add again 400g defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirs the 50min discharging, obtain the agent of protein gluing.
The protein gluing agent that obtains is used for the bonding of three layers of poplar plate, and carries out the test of dry strength and wet tenacity, recording respectively dry strength is that 1.85MPa and wet tenacity are 0.75MPa.
Comparative Examples 1
In a 2000mL there-necked flask, add 1000g water, then add 300 gram defatted soy flour (Guangzhou Hisoya Biological Science ﹠ Technology Co., Ltd., protein wt percentage composition 50%), stirred 30 minutes until albumen is dispersed in water fully, the mixed solution of gained is used for the bonding of three layers of poplar plate and carries out the test of dry strength and wet tenacity as sizing agent, and recording respectively dry strength is that 1.25MPa and wet tenacity are 0.45MPa.The dry strength of three layers of glued board is 1.25MPa, and 63 ℃ of lower wet tenacitys of soaking after 3 hours are 0.45MPa.
The dry strength of embodiment 1～5 and Comparative Examples 1 (MPa) and wet tenacity (MPa) data are as shown in table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | |
| Dry strength (MPa) | 1.88 | 2.55 | 2.46 | 1.78 | 1.85 | 1.25 |
| Wet tenacity (MPa) | 0.78 | 0.92 | 0.80 | 0.72 | 0.75 | 0.45 |
By the test data of table 1 as seen, add the solidifying agent of protein gluing of the present invention agent after, with respect to Comparative Examples 1, effectively improved bonding strength and the water tolerance of protein gluing agent.In the Comparative Examples 1, owing to do not add solidifying agent, thereby glue-line does not form cross-linked network structure behind the hot-press solidifying, sample is when the experiment of experience poach, uncrosslinked soluble small molecular and macromole can be soluble in water, effective adhesive substance in the glue-line is reduced, thereby water tolerance is very poor, can not satisfy the requirement of II class plate.The present invention utilizes the water tolerance of synthetic solidifying agent Enhancin matter sizing agent, forms cross-linked network structure and residual before solidifying-NH when key is hot-press solidifying
2More, acid anhydrides is active stronger, forms cross-linked network structure when more being conducive to solidify, and this cross-linked network structure is so that test specimen is more stable when poach is tested, thereby less to the destruction of glue-line.The dry strength of the glued board of three layers of poplar plate more than or equal to 0.72MPa, all satisfies the requirement of II class glued board more than or equal to 1.78MPa and wet tenacity in the embodiment of the invention 1～5.
Claims (10)
1. the preparation method of the solidifying agent of protein gluing agent may further comprise the steps:
1) after being mixed, acid and amine obtains water-soluble polymer solution through the first reaction in water;
In the described acid in carboxyl and the amine amino mol ratio be 0.5～1:1;
Described acid is Pidolidone, L-TARTARIC ACID, FUMARIC ACID TECH GRADE, L-Aspartic acid, maleic acid, 2-oxoglutaric acid, L-hydroxysuccinic acid, methylene-succinic acid, D-2-aminoadipic acid, L-2-aminoadipic acid, 2, the compound of 2-dimethylated pentanedioic acid, Methylpropanedioic acid or formula I structure;
Described amine is the compound of formula II structure or formula III structure;
Wherein, the n among the formula II is 1～700 integer; X is 1～10 integer in the formula III, and y is 1～10 integer;
2) water-soluble polymer solution that step 1) is obtained and acid anhydrides obtain the solidifying agent of protein gluing agent through the second reaction;
Mol ratio amino in described acid anhydrides and the amine is 0.2～10:1.
2. the preparation method of the solidifying agent of protein gluing according to claim 1 agent is characterized in that, in the step 1), and the first reaction conditions: at 120 ℃～190 ℃ lower reaction 1h～3h.
3. the preparation method of the solidifying agent of protein gluing according to claim 1 agent, it is characterized in that, step 2) in, described acid anhydrides is MALEIC ANHYDRIDE, Succinic anhydried, trimellitic acid 1,2-anhydride, norbornene dicarboxylic anhydride, the naphthalene acid anhydride, dimethyl maleic anhydride, Pyroglutaric acid, the diethylene triamine pentacetic acid (DTPA) dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, methylene radical tetrahydrophthalic anhydride in the methyl, tetrahydrophthalic anhydride, the tetrachloro-phthalic acid acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid anhydride, the 2-methyl maleic anhydride, HHPA, the chlorination trimellitic acid 1,2-anhydride, the phenylsuccinic acid acid anhydride, diacetyl oxide, in the Tetra hydro Phthalic anhydride one or more.
4. the preparation method of the solidifying agent of protein gluing according to claim 1 agent is characterized in that step 2) in, the second reaction conditions: at 20 ℃～70 ℃ lower reaction 1min～30min.
5. the preparation method of the solidifying agent of protein gluing according to claim 1 agent is characterized in that, the first reaction finishes rear or/and add water in the second reaction.
6. the preparation method of the solidifying agent of protein gluing according to claim 1 agent is characterized in that step 2) in, the aqueous sodium hydroxide solution of adding 0.5mol/L～1.5mol/L.
7. the solidifying agent of the protein gluing agent of each described preparation method preparation according to claim 1～6.
8. the application of the solidifying agent of protein gluing according to claim 7 agent in the agent of preparation protein gluing.
9. application according to claim 8 is characterized in that, the solidifying agent of described protein gluing agent and protein-based thing mix and blend 5min～60min obtain the agent of protein gluing;
Described protein-based thing is one or more in vegetable-protein, whey-protein, casein, the haemproteins.
10. application according to claim 9 is characterized in that, described vegetable-protein is one or more in legume protein, wheat gluten protein, zein, the cassava crude protein;
Described legume protein is a kind of in soybean protein isolate, textured soybean protein, low fat bean powder, the defatted soy flour.
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| CN 201110401679 CN102399515B (en) | 2011-12-07 | 2011-12-07 | Curing agent for protein adhesive, and preparation method and application of curing agent |
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| CN102911356B (en) * | 2012-10-16 | 2015-05-20 | 中国科学院宁波材料技术与工程研究所 | Bio-based water-soluble polymer solution, and preparation method and application thereof |
| WO2014207277A1 (en) | 2013-06-25 | 2014-12-31 | Foresa, Industrias Quimicas Del Noroeste, S.A.U. | Composition in an aqueous base, method for producing same, and use of said composition as a bioadhesive |
| CN104610909B (en) * | 2015-02-26 | 2017-04-12 | 许丽萍 | Aldehyde-free vegetable protein-based wood adhesive as well as preparation and application methods thereof |
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| CN101475790A (en) * | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
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| CN101475790A (en) * | 2008-01-04 | 2009-07-08 | 杨光 | Novel timber adhesive and preparation thereof |
Non-Patent Citations (2)
| Title |
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| 《大豆基木材胶粘剂的研究进展》;桂成胜等;《粘接》;20110410(第4期);67-72 * |
| 桂成胜等.《大豆基木材胶粘剂的研究进展》.《粘接》.2011,(第4期),67-72. |
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